Preparation of sulfurized phenol additives intermediates and compositions

Abstract

A process is described wherein olefins or acetylenic compounds are reacted with sulfurised intermediates to produce nitrile seal compatible additives. Olefin or acetylinic compound reaction with sulfurised compounds e.g. sulfurised phenols results in low chlorine additives. Also disclosed is a process for the production of low chlorine intermediates.

What is claimed is:  
     
       1. A process for preparing an oil-soluble sulfurised phenol additive compatible with nitrile seals which process comprises the steps of: 
       (i) reacting together at a temperature of at least 100° C.:  
       an oil-soluble active sulfur-containing sulfurised phenol intermediate; and an olefin or an acetylenic compound in an amount in excess of the stoichiometric amount required to react with the active-sulfur present in the sulfurized phenol intermediate; and  
       (ii) removing substantially all unreacted olefin or acetylenic compound; provided that, when the olefin is a mono-olefin, it is either unsubstituted aliphatic or is substituted with aromatic functionality, or with one or more hydroxy, amino, cyano, ester, amide carboxylic acid, carboxylate, alkaryl, amidine, sulfinyl, or sulfonyl groups.  
     
     
       2. A process as claimed in claim  1  wherein the olefin is: 
       (a) an acyclic olefin having at least two double bonds, adjacent double bonds being separated by two saturated carbon atoms; or  
       (b) an olefin comprising an alicyclic ring, which ring contains at least eight carbon atoms and at least two double bonds, each double bond being separated from the closest adjacent double bond(s) by two saturated carbon atoms.  
     
     
       3. A process as claimed in claim  2  wherein the olefin is a linear terpene. 
     
     
       4. A process as claimed in claim  3  wherein the terpene is geraniol. 
     
     
       5. A process as claimed in claim  2  wherein the olefin is 1,5-cyclooctadiene. 
     
     
       6. A process as claimed in claim  2  wherein the olefin comprises an alicyclic ring containing at least three double bonds, each end of each bond being separated from each adjacent double bond by two saturated carbon atoms. 
     
     
       7. A process as claimed in claim  6  wherein the olefin is 1,5,9-cyclododecatriene. 
     
     
       8. A process as claimed in claim  1  wherein the olefin is a mono-olefin. 
     
     
       9. A process as claimed in claim  8  wherein the mono-olefin is an α-olefin. 
     
     
       10. A process as claimed in claim  8  wherein the mono-olefin is a C 12  propylene tetramer. 
     
     
       11. A process as claimed in claim  8  wherein the mono-olefin is a compound containing a saturated alicyclic ring and one exocyclic double bond. 
     
     
       12. A process as claimed in claim  1  wherein the reaction in step (i) is carried out in the presence of a catalyst. 
     
     
       13. A process a claimed in claim  1  wherein the oil-soluble sulfurised phenol intermediate comprises less than 1000 ppm of chlorine and at least 4% by weight of sulfur and is made by: 
       a) reacting together sulfur monochloride and at least one phenol of general formula II                    
        wherein R represents a hydrocarbyl radical and y is an integer of 0 to 4, in a reaction mixture and at a temperature in the range of −50 to 250° C. wherein the mole ratio of-phenol: S 2 Cl 2  in the reaction mixture is greater than 1.7:1.  
     
     
       14. A process as claimed in claim  13  wherein the chlorine content is less than 800 ppm. 
     
     
       15. A process as claimed in claim  1  wherein the oil-soluble active sulfur-containing phenol intermediate is prepared from either sulfur monochloride, sulfur dichloride or mixtures thereof, and has a chlorine content of 100 ppm or greater. 
     
     
       16. An oil-soluble sulfurised phenol additive compatible with nitrile seals obtained by the process of claim  1 . 
     
     
       17. A lubricating oil composition which comprises lubricating oil as a major component and an oil-soluble sulfurised phenol additive as claimed in claim in  16 . 
     
     
       18. A lubricating oil concentrate which comprises one or more lubricant additives, an oil-soluble sulfurised phenol additive as claimed in claim  16  and lubricating oil. 
     
     
       19. A process as claimed in claim  1  wherein the amount of olefin or acetylenic compound is at least 100% in excess of the stoichiometric amount required to react with the active sulfur present in the sulfurised phenol intermediate. 
     
     
       20. A process as claimed in claim  1  wherein the amount of olefin or acetylenic compound is at least 400% in excess of the stoichiometric amount required to react with the active sulfur present in the sulfurised phenol intermediate. 
     
     
       21. A process as defined in claim  19  wherein substantially all unreacted olefin or acetylenic compound is removed so that unreacted olefin or acetylenic compound in the oil-soluble sulfurised phenol additive is 0.5% by weight or less. 
     
     
       22. A process as defined in claim  20  wherein substantially all unreacted olefin or acetylenic compound is removed so that unreacted olefin or acetylenic compound in the oil-soluble sulfurised phenol additive is 0.5% by weight or less. 
     
     
       23. An oil soluble, metal-free sulfurised phenol intermediate or additive of the formula:                    
       wherein R represents a hydrocarbyl radical having 1 to 50 carbon atoms, y is an integer of from 0 to 4 and may be different for each aromatic nucleus, n is an integer of 0 to 20, and x is an integer of from 1 to 4, with the proviso that the average number of carbon atoms per hydrocarbyl radical is sufficient to render said intermediate oil-soluble, said intermediate or additive having a chlorine content of less than 1000 ppm and a sulphur content of at least 4 mass %. 
     
     
       24. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  23  wherein the chlorine content is less than or equal to 900 and the sulfur content is from 4 to 16 mass %. 
     
     
       25. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  23  having a level of un-sulfurised phenolic material of up to 20 mass %. 
     
     
       26. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  24  having a level of un-sulfurised phenolic material of up to 20 mass %. 
     
     
       27. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  23  having a chlorine content of 500 ppm or less. 
     
     
       28. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  24  having a chlorine content of 500 ppm or less. 
     
     
       29. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  26  having a chlorine content of 500 ppm or less. 
     
     
       30. An oil-soluble, metal-free surfurised phenol intermediate or additive compatible with nitrile seals of claim  23  wherein the sulfur content is from 6 to 12 mass %. 
     
     
       31. An oil-soluble, metal-free surfurised phenol intermediate or additive compatible with nitrile seals of claim  29  wherein the sulfur content is from 6 to 12 mass %. 
     
     
       32. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  23  having an active sulfur content of up to 2.43 mass %. 
     
     
       33. An oil-soluble, metal-free sulfurised phenol intermediate or additive compatible with nitrile seals of claim  31  having an active sulfur content of up to 2.43 mass %. 
     
     
       34. A phenate or overbased phenate additive having a chlorine content of less than 1000 ppm prepared by reaction of an intermediate or additive of claim  23  with an alkali or alkaline earth metal salt or compound. 
     
     
       35. A phenate or overbased phenate additive having a chlorine content of less than 1000 ppm prepared by reaction of an intermediate or additive of claim  33  with an alkali or alkaline earth metal salt or compound. 
     
     
       36. A phenate or overbased phenate additive of claim  34  comprising a neutral or overbased calcium sulfurised phenate. 
     
     
       37. A phenate or overbased phenate additive of claim  35  comprising a neutral or overbased calcium sulfurised phenate. 
     
     
       38. A lubricating oil concentrate comprising 
       (a) lubricating oil; and  
       (b) at least one or more oil-soluble sulfurised phenol intermediates or additives of claim  34  present in the concentrate at a level such that a lubricating oil composition prepared from the concentrate comprises 100 ppm or less of chlorine.  
     
     
       39. A lubricating oil concentrate comprising 
       (a) lubricating oil; and  
       (b) at least one or more oil-soluble sulfurised phenol intermediates or additives of claim  35  present in the concentrate at a level such that a lubricating oil composition prepared from the concentrate comprises 100 ppm or less of chlorine.  
     
     
       40. A lubricating oil concentrate of claim  39  further comprising one or more ashless dispersants prepared from non-halogenated polymers. 
     
     
       41. A lubricating oil concentrate of claim  38  further comprising one or more ashless dispersants prepared from non-halogenated polymers. 
     
     
       42. A lubricating oil composition comprising 
       (a) oil of lubricating viscosity; and  
       (b) one or more oil-soluble sulfurised phenol intermediates or additives of claim  34 ;  
       the chlorine content of the lubricating oil composition being not more than 100 ppm. 
     
     
       43. A lubricating oil composition comprising 
       (a) oil of lubricating viscosity; and  
       (b) one or more oil-soluble sulfurised phenol intermediates or additives of claim  35 ;  
       the chlorine content of the lubricating oil composition being not more than 100 ppm. 
     
     
       44. A lubricating oil composition of claim  42  additionally comprising one or more ashless dispersants prepared from non-halogenated polymers. 
     
     
       45. A lubricating oil composition of claim  43  additionally comprising one or more ashless dispersants prepared from non-halogenated polymers. 
     
     
       46. A method of prolonging the life of elastomeric seals or of reducing ring sticking or both in heavy duty diesel engines which comprises lubricating the engine with an oil-soluble sulfurised phenol additive of claim  23 . 
     
     
       47. A method of prolonging the life of elastomeric seals or of reducing ring sticking or both in heavy duty diesel engines which comprises lubricating the engine with a lubricating oil concentrate of claim  38 . 
     
     
       48. A method of prolonging the life of elastomeric seals or of reducing ring sticking or both in heavy duty diesel engines which comprises lubricating the engine with a lubricating oil composition of claim  38 . 
     
     
       49. A method of lubricating a heavy duty diesel engine comprising lubricating the engine with a lubricating oil composition of claim  42  containing up to 3 mass % of the sulfurised phenol. 
     
     
       50. The method of claim  49  wherein the composition is exposed to nitrile seals. 
     
     
       51. An oil-soluble sulfurised phenol additive having a chlorine content of less than 1000 ppm and a delta tensile strength loss of no greater than 46% and/or a delta elongation at break loss of no greater than 46% measured on nitrile elastomers according to test methods DIN 53521 and DIN 53504.